Computational and Theoretical Chemistry最新文献

{"title":"Regulating fluorescent properties and ESIPT behavior of novel scaffold-based fluorescent molecule by different substituents: A TD-DFT study","authors":"Feiyang Yin,&nbsp;Hua Fang","doi":"10.1016/j.comptc.2025.115278","DOIUrl":"10.1016/j.comptc.2025.115278","url":null,"abstract":"<div><div>Recently, a new fluorophore 5-bis(benzo[<em>d</em>]thiazol-2-yl)phenol (BTP) is synthesized experimentally, and BTP-based probe can successfully recognize cysteine (Cys) quickly and sensitively (<em>Spectrochim. Acta Part A 217 (2019) 1–7</em>). Via introducing the –CN and/or –N(CH₃)₂ groups into BTP, three novel compounds (BTP-1, BTP-2 and BTP-3) are designed to investigate the substituent effects on the photophysical properties and excited state intramolecular proton transfer (ESIPT) process of BTP. The structural parameters, infrared (IR) vibrational spectra, electron densities and reduced density gradient (RDG) isosurfaces obtained by density functional theory (DFT) and time-dependent DFT (TD-DFT) methods have indicated that the intramolecular hydrogen bonds (IHBs) of BTP derivatives became stronger in the excited (S₁) state. The introduction of substituent leads to a bathochromic-shift of the absorption and fluorescence peaks. Meanwhile, from the potential energy curves, it can be found that the introduction of two –CN groups can effectively decrease the ESIPT energy barrier of BTP, while the coexistence of –CN and –N(CH₃)₂ hinder the ESIPT process.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115278"},"PeriodicalIF":3.0,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144070900","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electronic structure correction via DFT+U+mBJ, ferroelectricity, n-type half-metallicity, and high figure of merit in B/C/N/F-substituted BaTiO3","authors":"M. Usama ,&nbsp;Bassem F. Felemban ,&nbsp;Hafiz Tauqeer Ali ,&nbsp;S. Nazir","doi":"10.1016/j.comptc.2025.115275","DOIUrl":"10.1016/j.comptc.2025.115275","url":null,"abstract":"<div><div>The various features of the pristine (prist.)/X = B/C/N/F@O-substituted (subst.) BaTiO<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span> (BTO) perovskite oxide are investigated through <span><math><mrow><mi>a</mi><mi>b</mi></mrow></math></span>-<span><math><mrow><mi>i</mi><mi>n</mi><mi>i</mi><mi>t</mi><mi>i</mi><mi>o</mi></mrow></math></span> calculations. It is revealed that the prist. motif is a non-magnetic insulator keeping an bandgap (<span><math><msub><mrow><mi>E</mi></mrow><mrow><mi>g</mi></mrow></msub></math></span>) of 3.5 eV for GGA<span><math><mrow><mo>+</mo><mi>U</mi><mo>+</mo></mrow></math></span>mBJ, which is in 100% accordance with the experimental one and contains a spontaneous polarization (P) of 28 <span><math><mi>μ</mi></math></span>Ccm⁻². It is found that the X-substitution has a negative influence on structural distortions, resulting in lower P. The most astonishing feature is that the F@O-subst. BaO-layer-based structure displays an <span><math><mi>n</mi></math></span>-type half-metallic (HM) character holding a giant <span><math><msub><mrow><mi>E</mi></mrow><mrow><mi>g</mi></mrow></msub></math></span> of 3.3 eV in the spin-majority channel, which is large enough to prevent reverse leakage current and guarantee the HM state. Strikingly, a high figure of merit of 1.04/1.05 at 300 K makes the prist./F@O-subst. BaO-layer-based structure, valuable for designing the thermoelectric devices.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115275"},"PeriodicalIF":3.0,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144083728","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Quantum chemistry and molecular dynamics study on the intermolecular interactions and stability of NL24 and MTNP complexes","authors":"Zeyuan Chen ,&nbsp;Junjun Zhao ,&nbsp;Shuangfei Zhu ,&nbsp;Guangrui Liu ,&nbsp;Shuhai Zhang","doi":"10.1016/j.comptc.2025.115282","DOIUrl":"10.1016/j.comptc.2025.115282","url":null,"abstract":"<div><div>1,2-bis(4,5-di(1H-tetrazol-5-yl)-2H-1,2,3-triazol-2-yl)diazene (NL24), a recently synthesized energetic material with great potential, exhibits superior detonation performance and environmentally friendly decomposition products. However, its relatively high sensitivity remains a challenge for application. To reduce the sensitivity of NL24 and enhance its prospects of application, the feasibility of forming complexes between NL24 and the insensitive explosive 1-methyl-3,4,5-trinitropyrazole (MTNP) is investigated through quantum chemistry calculations and molecular dynamics simulations. Additionally, the effects of MTNP on the stability of NL24 are studied. The research results indicate that the formation of intermolecular hydrogen bonds and the contribution of van der Waals interactions are identified as the main factors enabling stable complex formation between NL24 and MTNP. Among the four potential NL24/MTNP dimer configurations, Configuration 1 exhibits the highest stability. Electrostatic and dispersion effects play dominant roles in the binding interaction. Furthermore, the stability of NL24 is effectively improved after forming a complex with MTNP.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115282"},"PeriodicalIF":3.0,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144070899","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A fullerene-based strategy to enhance para-aminobenzoic acid permeability in skin cancer treatment: DFT and molecular dynamic study","authors":"Ali Muneer ,&nbsp;Baraa Abd Al Kareem Al Saray ,&nbsp;Mustafa M. Kadhim ,&nbsp;Waleed Khalid Al-Azzawi ,&nbsp;Wesam Radhi Kadhum","doi":"10.1016/j.comptc.2025.115280","DOIUrl":"10.1016/j.comptc.2025.115280","url":null,"abstract":"<div><div>Using nanomaterials to alter pharmaceutical molecules can significantly enhance how well drugs are absorbed and how long they remain stable in the body. There's a lot of research showing that this approach has been successful and holds great potential for improving medication effectiveness. Solubility and diffusion are usually affected by how the drug and nanocarrier interact with each other. A compound should be better able to pass biological membranes if it dissolves more easily in lipids. Still, the effects of these changes on solubility dynamics and permeability have not been well studied. We introduce the idea of “targeted lipid solubility enhancement” and look into how it works to improve the pharmacological properties of PABA that has been loaded onto a functionalized fullerene. We use DFT calculations and MD simulations to look at how changes in the structure affect the molecule's stability and how it moves in different situations. The findings show that altering the way the chemical compound and the nanocarrier work together can make it easier for the compound to move through a membrane. This improvement can occur even when the compound and the nanocarrier generally prefer to stay connected closely. Our findings highlight a targeted enhancement of lipid solubility, specifically designed to improve para-aminobenzoic acid (PABA) permeability across lipid-rich skin barriers.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115280"},"PeriodicalIF":3.0,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143948819","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Machine learning-based analysis of electronic properties as predictors of anticholinesterase activity in chalcone derivatives","authors":"Thiago Buzelli ,&nbsp;Bruno Ipaves ,&nbsp;Felipe Gollino ,&nbsp;Wanda Pereira Almeida ,&nbsp;Douglas Soares Galvão ,&nbsp;Pedro Alves da Silva Autreto","doi":"10.1016/j.comptc.2025.115268","DOIUrl":"10.1016/j.comptc.2025.115268","url":null,"abstract":"<div><div>In this study, we investigated the correlation between the electronic properties of anticholinesterase compounds and their biological activity. While this correlation has been effectively explored in previous studies, we employed a more advanced approach: machine learning. We analyzed a set of 22 molecules sharing a similar chalcone skeleton, categorizing them into two groups based on their IC₅₀ indices: high and low activity. Using the open-source software Orca, we calculated the geometries and electronic structures of these molecules. Over a hundred parameters were extracted, including Mulliken and Lowdin electronic populations, molecular orbital energies, and Mayer’s free valences, forming the foundation for machine learning features. Through our analysis, we developed models capable of distinguishing between the two groups. Notably, the most informative descriptor relied solely on electronic populations and orbital energies. Identifying computationally relevant properties for biological activity enhances drug development efficiency, saving time and resources.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1249 ","pages":"Article 115268"},"PeriodicalIF":3.0,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949088","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the ground and low-lying excited states of gatifloxacin","authors":"Iuri N. Soares ,&nbsp;Gabriel L.C. de Souza","doi":"10.1016/j.comptc.2025.115258","DOIUrl":"10.1016/j.comptc.2025.115258","url":null,"abstract":"<div><div>In this work, we present an investigation on the photoinduced degradation of the micropollutant gatifloxacin (GFX). Ground state properties (such as bond lengths, hydrogen-bond interactions, and relative energies) for one protonated and two deprotonated forms of the compound were determined through the use of the density functional theory (DFT), while time-dependent DFT (TD-DFT) was used for probing their excited state parameters (vertical excitation energies, oscillator strengths — OS, and structures). The CAM-B3LYP, M06-2X, and LC-<span><math><mi>ω</mi></math></span>PBE exchange–correlation functionals were employed along with the 6-311+G(d,p), 6-311++G(d,p), def2-TZVP, and aug-cc-pVTZ basis sets. Solvent effects were incorporated with the polarizable continuum model. Considering the parent GFX molecule as instance, all the results for its ground state computed using the CAM-B3LYP exchange–correlation functional with a given basis set were found to be in excellent agreement to those corresponding determined using the M06-2X along with any of the basis sets used; excellent agreement was also observed in the case of the excited state properties. Three states (S₁, S₄, and S₅) were probed to be likely accessible among the five lowest-lying excited singlets, with S₁ being determined at 4.22 eV with OS = 0.1159, S₄ at 4.60 eV with OS = 0.7243, and S₅ at 4.94 eV with OS = 0.1672, at the CAM-B3LYP/6-311+G(d,p) level of theory in water, for example. These results were used for establishing a correlation with the findings presented in previous (recent) experimental work involving the photoinduced degradation of the GFX molecule. In this sense, S₁ was assigned as the excited state connected to the degradation path of the GFX molecule when irradiated with the UVA light while the existence of two additional excited singlet states with non-zero OS (S₄ and S₅, with S₄ having a considerably large OS) was associated to the faster degradation provided by the more energetic UVC when compared to the UVA radiation. In addition, the excited state structures suggested GFX as undergoing photodecomposition (chemical reactions occurring in the excited state) rather than direct photolysis when irradiated with UVA and UVC light.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1249 ","pages":"Article 115258"},"PeriodicalIF":3.0,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143937081","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical investigation of the energy transmission mechanism in phthalocyanine-benzimidazole photosensitizers used for singlet oxygen generation","authors":"Sérgio H.D.M. Faria,&nbsp;Roberto L.A. Haiduke","doi":"10.1016/j.comptc.2025.115274","DOIUrl":"10.1016/j.comptc.2025.115274","url":null,"abstract":"<div><div>The present work is focused on investigating the spatial factors regarding the energy transmission mechanism occurring in four second-generation phthalocyanine-benzimidazole photosensitizers proposed for singlet oxygen production (H₂Pc, ZnPc, GaClPc and InClPc) through analyses from the Quantum Theory Atoms in Molecules (QTAIM). Hence, electron and spin densities obtained by means of Density Functional Theory (DFT) are considered here. The QTAIM quantities calculated for these phthalocyanines allowed us to investigate the atoms presenting the most relevant variations in the electronic structure moving from the singlet ground state to the first triplet excited state, <span><math><msub><mi>S</mi><mn>0</mn></msub><mo>→</mo><msub><mi>T</mi><mn>1</mn></msub></math></span>, indicating the regions of the photosensitizers where the transmission of energy from these molecules to oxygen (O₂) could take place. This analysis was corroborated by spin densities that pointed out the positions where the highest rates of singlet oxygen formation would take place. Hence, the nitrogen and mainly carbon atoms from the inner phthalocyanine ring are pointed as the docking sites for energy transmission aiming singlet oxygen generation from phthalocyanine-benzimidazole photosensitizers. Finally, while the spatial features seen in metallophthalocyanines remain similar for all metals in the oxidation states considered here [Zn(II), Ga(III) and In(III)], the H₂Pc compound shows small differences with the respect.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1249 ","pages":"Article 115274"},"PeriodicalIF":3.0,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143937164","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electronic and photocatalytic characteristics of van der Waals MoSeTe/GaSe Heterostructures","authors":"Celal Yelgel","doi":"10.1016/j.comptc.2025.115272","DOIUrl":"10.1016/j.comptc.2025.115272","url":null,"abstract":"<div><div>Identifying an efficient photocatalyst is essential for tackling energy scarcity and environmental pollution. Two-dimensional (2D) materials have attracted considerable interest owing to their remarkable electronic, optical, and mechanical characteristics. They are regarded as potential alternatives to Si-based semiconductors. 2D materials exhibit significant potential as effective candidates for highly efficient photocatalysis. This results from their exceptionally high surface area and the minimal distance charge carriers must traverse. Gallium monochalcogenides (GaX where X = S, Se, Te) and Janus transition metal dichalcogenides, which consist of two different chalcogenides (S, Se, or Te) paired with a single transition metal (Mo, W, Pt, etc.), are increasingly recognized for their potential in photocatalytic water splitting. This recognition is attributed to their advantageous band gap and remarkable stability. In this present work, we study the electronic band structure, photocatalytic properties, and stability of a novel van der Waals MoSeTe/GaSe heterostructure based on first-principles calculations. The MoSeTe/GaSe heterostructure demonstrates potential as a photocatalyst for overall water splitting, attributed to the effects of the built-in electric field. The built-in electric field at the interface effectively separates photogenerated carriers. Our results reveal that the energetically stable MoSeTe/GaSe heterostructure exhibits a type-I band alignment, which promotes the spatial confinement of photogenerated electron-hole pairs a favourable feature for enhanced radiative recombination, making it suitable for optoelectronic applications. Notably, the heterostructure possesses an indirect band gap of 0.881 eV. The lattice mismatch rate is 0.68 %, and the binding energy is calculated at 7.5 meV/atom, suggesting thermodynamically favourable. The band edge encompasses the redox potential of water, suggesting that the heterostructure can facilitate hydrogen production through the photocatalytic decomposition of H₂O. The research has resulted in the development of a novel group of materials with significant potential for photocatalytic applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1249 ","pages":"Article 115272"},"PeriodicalIF":3.0,"publicationDate":"2025-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143904363","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Investigation of the detection of Thioguanine anti-cancer drug by using of X12O12 (X = mg, Zn) nanocage","authors":"Mustafa Habeeb Chyad ,&nbsp;Abdulrahman T. Ahmed ,&nbsp;Gaurav Sanghvi ,&nbsp;Subbulakshmi Ganesan ,&nbsp;Aman Shankhyan ,&nbsp;T. Krithiga ,&nbsp;Aziz Kubaev ,&nbsp;Rajashree Panigrahi ,&nbsp;Ahmed Mahal ,&nbsp;Hadil Faris Alotaibi","doi":"10.1016/j.comptc.2025.115270","DOIUrl":"10.1016/j.comptc.2025.115270","url":null,"abstract":"<div><div>Nanomaterials play a vital role in pharmaceutical research, particularly in cancer treatment like Thioguanine (TG). This study aimed to investigate how sensitive MgO and ZnO nanocages are in detecting TG through application of density functional theory (DFT). Various analyses have been executed, including examinations of sensor mechanism, non-covalent interactions (NCI), natural bond orbitals (NBO), frontier molecular orbitals (FMOs), and adsorption energy (E_ads). Nitrosourea adsorption on ZnO demonstrates the highest E_ads values at −53.98 kcal/mol, whereas MgO complexes exhibit lower E_ads. Energy gaps (E_g) of MgO and ZnO decline from 6.76 eV and 5.98 eV, respectively, compared to bare nanocage, revealing potential for utilizing these cages in Thioguanine detection. Analysis of frontier molecular orbitals indicates that 6 m-ZnO@TG complex exhibits the smallest E_g at 2.33 eV among all designed complexes. Additionally, recovery time of TG from MgO nanocages is notably shorter compared to ZnO nanocages. Topological analysis suggests a non-covalent interaction between ZnO and MgO nanocages. Furthermore, electrical conductivity values rise following the adsorption process. ZnO complex exhibits the highest electrical conductivity. Sensor mechanism demonstrates heightened sensitivity in ZnO complexes attributed to their narrow energy gaps. Consequently, ZnO stands out as a promising candidate for detecting TG and as a delivery system for TG in cancer treatment.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1249 ","pages":"Article 115270"},"PeriodicalIF":3.0,"publicationDate":"2025-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143906532","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Probing the molecular and electronic structures of higher transition metal carbonyls [Ru(CO)4SiX] (X = O, S, Se, Te): A DFT study","authors":"Arun Ramamurthy ,&nbsp;Sharmila Kumarasamy ,&nbsp;Deepa Masilamani","doi":"10.1016/j.comptc.2025.115269","DOIUrl":"10.1016/j.comptc.2025.115269","url":null,"abstract":"<div><div>Through the DFT calculations, Axial and Equatorial isomers of [Ru(CO)₄SiX] (X = O, S, Se, Te) were investigated using B3LYP level of theory. The obtained energetic values show that stability of axial isomer of [Ru(CO)₄SiX] is more than equatorial isomer of [Ru(CO)₄SiX]. From NPA and EDA analysis, we have obtained the bonding nature of this carbonyl complex. Hardness (ƞ) value obtained from FMO study decreases while changing the X from O to Te, which also reflected in the HOMO-LUMO energy gap whose values lies in the range of 3.96–5.12 eV. The WBI analysis indicates a bond index of Ru<img>Si bond. NBO analysis reveals that contribution from Ru is less in Ru<img>Si bond than Si. Similarly, the contribution from C is more than Si in the carbonyl group.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1249 ","pages":"Article 115269"},"PeriodicalIF":3.0,"publicationDate":"2025-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143906530","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}